CN108654695A - 吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂及制备方法及应用 - Google Patents

吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂及制备方法及应用 Download PDF

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CN108654695A
CN108654695A CN201710197166.0A CN201710197166A CN108654695A CN 108654695 A CN108654695 A CN 108654695A CN 201710197166 A CN201710197166 A CN 201710197166A CN 108654695 A CN108654695 A CN 108654695A
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王建辉
段玉莲
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Abstract

本发明公开了吲哚[3,2‑a]恶唑烷标记的钌卡宾催化剂及制备方法及应用，吲哚[3,2‑a]恶唑烷标记的钌卡宾催化剂，其特征是用式(II)所示：

Description

吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂及制备方法及应用
技术领域
本发明属过渡金属有机催化剂领域，涉及一种吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂及制备方法及应用。
背景技术
为了解决均相烯烃复分解催化剂在反应完成后难以从混合物中分离出来的问题，近年来人们合成了一系列离子标记，氟标记以及氧化还原开关标记的可回收钌烯烃复分解催化剂[1-6]。此外，人们还有利用硅基材料、聚合物和磁性纳米粒子制备了负载型钌催化剂[2-9]。
这些系统需要昂贵的离子液体作为载体材料，导致异质性，并因此降低随后反应中的反应速率。此外，这些方法常常在再循环的催化剂中产生杂质，例如已分解的催化剂，这可能加速未来反应中的催化剂分解等诸如此类问题。
发明内容
本发明的目的是为了克服现有技术的不足，提供一种吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂。
本发明的第二个目的是提供一种吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂的制备方法。
本发明的第三个目的是提供一种吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂催化闭环和交叉复分解反应中的应用。
本发明的第四个目的是提供一种吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂的回收方法。
本发明的技术方案概述如下：
吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂，是用式(II)所示：
上述吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂的制备方法，包括如下步骤：
氮气保护下，将Grubbs II催化剂(III)、氯化亚铜和化合物(I)溶于二氯甲烷中，在搅拌下，加热回流25-35min，降温至室温，旋干，过色谱硅胶柱，向所述色谱硅胶柱内加入体积比为1:2的石油醚和二氯甲烷的混合液洗脱杂质，再加入二氯甲烷做洗脱得到吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂(II)，反应式如下：
所述Grubbs II催化剂的结构见(III)：
优选地，Grubbs II催化剂，氯化亚铜和化合物(I)的摩尔比为1:1:1.25
上述吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂在催化闭环和交叉复分解反应中的应用。
本发明的优点：
本发明的吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂在催化闭环和交叉复分解反应中催化效率高，催化剂回收后可以重复使用，降低了成本，减少了污染。
具体实施方式
下面结合具体实施例对本发明作进一步的说明。
化合物(I)(吲哚[3,2-a]恶唑烷配体)，用式(I)所示：
实施例1
化合物I的合成：
1)在圆底烧瓶中氮气保护下，将化合物IV,命名为：1-(2-羟乙基)-2,3,3-三甲基-3H-吲哚-1-鎓溴化物(2g)和化合物V，命名为：(E)-4-异丙氧基-3-(1-烯丙基)苯甲醛(1.53g)溶于乙醇中，并滴加3滴甲基磺酸作为催化剂。回流8h，旋干溶剂，乙酸乙酯\正己烷混合洗旋干后的残余物，得橙黄色固体。
2)再将上述得到橙黄色固体溶于50mL的5％的氢氧化钾的水溶液中，用乙酸乙酯萃取(3x30mL)，无水硫酸镁干燥，旋干，得黄色固体I。
1H NMR(400MHz,CDCl3)δ7.57(s,1H),7.33–7.27(m,1H),7.21(t,J＝7.6Hz,1H),7.13(d,J＝7.2Hz,1H),6.99(t,J＝7.5Hz,1H),6.92–6.82(m,3H),6.75(d,J＝15.9Hz,1H),6.31(dq,J＝13.4,6.5Hz,1H),6.20(d,J＝15.9Hz,1H),4.58(dq,J＝11.6,5.8Hz,1H),3.91–3.45(m,5H),1.96(d,J＝6.5Hz,3H),1.50(s,3H),1.40(d,J＝6.0Hz,6H),1.22(s,3H).13C NMR(101MHz,CDCl3)δ154.58(s),150.70(s),139.89(s),131.99(s),129.05(s),128.40(s),127.55(s),126.39(s),126.08(s),125.75(s),124.89(s),123.47(s),122.41(s),121.65(s),114.33(s),112.03(s),110.07(s),70.99(s),63.51(s),50.13(s),47.92(s),28.47(s),28.10(s),22.21(s),20.35(s),18.96(s)
化合物1的合成路线
吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂，用式(II)所示：
实施例2
吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂的制备方法，包括如下步骤：
氮气保护下，Grubbs II催化剂(III)(1.86g,2.2mmol)和氯化亚铜(0.220g，2.2mmol)和化合物I(1.16g,2.75mmol)溶于25mL二氯甲烷中，在搅拌下，加热回流30min，降温至室温，旋干，过色谱硅胶柱，向所述色谱硅胶柱内加入体积比为1:2的石油醚和二氯甲烷的混合液洗脱杂质，再加入二氯甲烷洗脱得到1g绿色固体。
所述Grubbs II催化剂的结构见(III)：
经检测，1H NMR(400MHz,CDCl3):δ16.54(s,1H),7.57(d,J＝8.4Hz,1H),7.20–6.99(m,7H),6.86–6.69(m,3H),6.00(d,J＝15.9Hz,1H),4.91(m,J＝12.3,6.1Hz,1H),4.20(s,4H),3.89–3.36(m,4H),2.42(t,J＝30.6Hz,18H),1.44(s,3H),1.29(d,J＝5.9Hz,6H),1.18(s,3H). 13C NMR(101MHz,CDCl3):δ211.04,152.10,149.37,145.43,141.71,138.83,131.15,130.81,129.41,127.99,127.46,126.52,124.52,122.87,120.24,112.99,109.94,63.58,53.44,50.06,48.13,30.84,28.17,27.30,26.01,21.09,20.14.MS(ESI)m/z CalcdFor[C45H52ClN3O2Ru][M-2Cl+H]+ 803.2792,found 804.2892.Anal.Calcd.forC45H52Cl3N3O2Ru:C 61.74,H 6.10,N 4.80；Found:C 61.89,H 6.23,N 4.76.CCDC:1458091为吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂(II)。
实施例3
吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂(II)(下面实施例中简称为催化剂II)在闭环交叉复分解反应中的应用
4-丙二酸二乙酯基环戊烯(化合物2)的合成：
在40℃条件下，将二烯丙基丙二酸二乙酯(化合物1)(24mg(0.1mmol)和0.875毫克(1mol％)催化剂II加入1mL的二氯甲烷，搅拌。反应7min，旋干反应溶剂后提纯产品，产率为90％，经核磁确定，1H NMR(400Hz,CDCl3):δ5.59(s,2H),4.18(q,J＝7.1Hz,4H),3.00(s,4H),1.23(t,J＝7.1Hz,6H).13C NMR(100MHz,CDCl3):δ172.16,127.77,61.46,58.80,40.80,13.98.产物是4-丙二酸二乙酯基环戊烯(化合物2)。
实施例4
1-(4-甲基苯磺酰基)-2,5-二氢-1H-吡咯(化合物4)的合成，操作同实施例3，反应原料之一为化合物3(催化剂用量、反应时间及产率，见表1)
1H NMR(400MHz,CDCl3):δ7.72(dd,J＝8.2,1.6Hz,2H),7.32(d,J＝7.6Hz,2H),5.65(s,2H),4.11(d,J＝2.1Hz,4H),2.42(d,J＝1.8Hz,3H).13C NMR(100MHz,CDCl3):δ143.49,134.23,129.79,127.40,125.46,54.86,21.52.
实施例5
1-(甲苯-4-磺酰基)-2,5-二氢-3-甲基吡咯(化合物6)的合成，操作同实施例3，反应原料之一为化合物5(催化剂用量、反应时间及产率，见表1)
1H NMR(400MHz,CDCl3):δ7.72(t,J＝6.5Hz,2H),7.32(d,J＝7.9Hz,2H),5.25(d,J＝1.4Hz,1H),4.01(d,J＝40.1Hz,4H),2.42(d,J＝6.1Hz,3H),1.65(s,3H).13C NMR(100MHz, CDCl3):δ143.40,135.05,134.22,129.75,127.41,119.08,57.69,55.15,21.50,14.04.
实施例6
1-(甲苯-4-磺酰基)-2,3,6-三氢吡啶(化合物10)的合成，操作同实施例3，反应原料之一为化合物9(催化剂用量、反应时间及产率，见表1)
1H NMR(400MHz,CDCl3):δ7.69(d,J＝7.2Hz,2H),7.34(d,J＝7.9Hz,2H),5.83–5.55(m,2H),3.59(d,J＝1.9Hz,2H),3.27–3.11(m,2H),2.45(s,3H),2.28–2.14(m,2H).13CNMR(100MHz,CDCl3):δ143.52,133.39,129.64,127.69,125.07,122.77,44.79,42.66,25.28,21.52.
实施例7
1-(甲苯-4-磺酰基)-2,3,6,7-四氢-1H吖庚因(化合物12)的合成，操作同实施例3，反应原料之一为化合物11(催化剂用量、反应时间及产率，见表1)
1H NMR(400MHz,CDCl3):δ7.68(d,J＝8.1Hz,2H),7.31(d,J＝8.0Hz,2H),5.81–5.71(m,2H),3.35–3.21(m,4H),2.42(s,3H),2.32(d,J＝4.7Hz,4H).13C NMR(100MHz,CDCl3):δ159.03,136.29,128.99,128.04,127.61,125.92,124.15,121.66,71.30,31.99.
实施例8
2,5-二氢苯并恶庚英(化合物14)的合成，操作同实施例3，反应原料之一为化合物13(催化剂用量、反应时间及产率，见表1)
1H NMR(400MHz,CDCl3):δ7.41–7.13(m,4H),6.07–5.90(m,1H),5.64–5.55(m,1H),4.72(dd,J＝4.8,2.4Hz,2H),3.64(d,J＝2.7Hz,2H).13C NMR(100MHz,CDCl3):δ159.03,136.29,128.99,128.04,127.61,125.92,124.15,121.66,71.30,31.99.
实施例9
4-甲基-2,5-二氢苯并恶庚英(化合物16)的合成，操作同实施例3，反应原料之一为化合物15(催化剂用量、反应时间及产率，见表1)
1H NMR(400MHz,CDCl3):δ7.37–7.29(m,1H),7.26–7.12(m,3H),5.40(d,J＝1.0Hz,1H),4.70(dd,J＝3.2,1.6Hz,2H),3.60(s,2H),2.01(s,3H).13C NMR(100MHz,CDCl3):δ158.86,134.97,134.07,129.19,128.04,123.67,121.26,70.40,37.39,26.30.
实施例10
2,5-二氢-1H吡咯基苯基甲酮(化合物18)的合成，操作同实施例3，反应原料之一为化合物17(催化剂用量、反应时间及产率，见表1)
1H NMR(400MHz,CDCl3):δ7.21–7.09(m,2H),7.02(d,J＝2.7Hz,3H),5.48(s,1H),5.34(d,J＝1.5Hz,1H),4.04(s,2H),3.77(s,2H).13C NMR(100MHz,CDCl3):δ169.26,136.57,129.59,128.06,126.60,125.33,55.45,53.14.
实施例11
1-(甲苯-4-磺酰基)-2,5-二氢-3，4-二甲基吡咯(化合物8)的合成，操作同实施例3，反应原料之一为化合物7(催化剂用量、反应时间及产率，见表1)
在80℃条件下，将二烯丙基丙二酸二乙酯(279mg(1mmol)和0.875毫克(1mol％)催化剂II加入1mL的二氯甲烷，搅拌。反应7min，旋干反应溶剂后提纯产品，产率为90％，经核磁确定，1H NMR(400MHz,CDCl3):δ7.73(d,J＝8.0Hz,2H),7.34(d,J＝7.8Hz,2H),3.99(s,4H),2.44(s,3H),1.56(s,6H).13C NMR(100MHz,CDCl3):δ143.29,134.30,129.72,127.49,126.21,58.83,21.52,11.12.
实施例12
吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂(II)在交叉复分解反应中的应用
苯甲酸肉桂酯(化合物21)的合成(产率，见表1)
在40℃条件下，将苯甲酸烯丙酯(化合物19,16.2mg,0.1mmol)、苯乙烯(化合物20,20.8mg，0.2mmo)和0.875mg(1mol％)催化剂II加入1ml的二氯甲烷，搅拌，反应12min，旋干反应溶剂后提纯产品，产率为89％，经核磁确定1H NMR(400Hz,CDCl3):δ8.12(d,J＝7.22Hz,2H),7.60(t,J＝7.38Hz,2H),7.44-7.50(q,J＝7.51Hz,2H),7.36(t,J＝7.19Hz,1H),7.29(t,J＝7.10Hz,1H),6.78(d,J＝16.0Hz,4H),6.40-6.44(m,1H),5.02(dd,J＝6.39Hz and J＝0.97Hz,3H).
表1为催化剂II对不同底物催化活性测试实验a
表头及表中：
a此反应溶液浓度为0.1M(其中，化合物7底物浓度为1M)；
b产率为分离产率；
c此反应在100℃的甲苯溶液中反应。
参考文献
[1]D.J.Cole-Hamilton,Science,2003,299,1702–1706.
[2](a)D.Y.Wu,M.Marzini,E.Lindner and H.A.Z.Mayer,Anorg.Allg.Chem.2005,631,2538–2539；(b)F.Gelman,J.Blum and D.Avnir,J.Am.Chem.Soc.2002,124,14460–14463；(c)R.Akiyama and S.Kobayashi,Angew.Chem.2002,114,2714–2716；Angew.Chem.Int.Ed.2002,41,2602–2604；(d)R.Akiyama and S.Kobayashi,Angew.Chem.2001,113,3577–3579；Angew.Chem.Int.Ed.2001,40,3469–3471.
[3]V.K.Dioumaev and R.M.Bullock,Nature.2003,424,530–532.
[4](a)P.M.Mauduit and K.Grela,Chem.Soc.Rev.2008,37,2433–2442；(b)R.I.Kmentováand S.Toma,Green Chem.2008,10,484–496；(c)W.Miao andT.H.Chan,Acc.Chem.Res.2006,39,897–908.
[5](a)M.Matsugi and D.P.Curran,J.Org.Chem.2005,70,1636–1642；b)Q.Yaoand Y.Zhang,J.Am.Chem.Soc.2004,126,74–75；(c)M.Wende and J.A.Gladysz,J.Am.Chem.Soc.2003,125,5861–5872；(d)I.T.Horváth and J.Rábai,Science.1994,266,72–75.
[6](a)G.-Y.Liu,H.He and J.-H.Wang,Adv.Synth.Catal.2009,351,1610–1620；(b)M.Süβner and H.Plenio,Angew.Chem.Int.Ed.2005,117,7045–7048；Angew.Chem.Int.Ed.2005,44,6885–6888.
[7](a)H.Zhou,Y.M.Wang,W.Z.Zhang,J.P.Qu and X.B.Lu,Green Chem,2011,13,644–650；(b)H.Q.Yang,G.Li,Z.C.Ma,J.B.Chao and Z.Q.Guo,J.Catal.,2010,276,123–133；(c)H.Q.Yang,X.J.Han,G.Li and Y.W.Wang,Green Chem,2009,11,1184–1193；(d)D.P.Allen,M.M.V.Wingerden and R.H.Grubbs,Org.Lett.,2009,11,1261–1264；(e)M.Wang,P.Li and L.Wang,Eur.J.Org.Chem.,2008,2255–2261；(f)H.Qiu,S.M.Sarkar,D.H.Lee and M.J.Jin,Green Chem.,2008,10,37–40.
[8](a)D.B.Bagal,Z.S.Qureshi,K.P.Dhake,S.R.Khan and B.M.Bhanage,GreenChem.,2011,13,1490–1494；(b)Y.Wang,J.H.Liu and C.G.Xia,Adv.Synth.Catal.,2011,353,1534–1542；(c)B.Karimi and P.F.Akhavan,Chem.Commun.,2009,3750–3752；(d)O.Kuhl,Chem.Soc.Rev.,2007,36,592–607.
[9](a)H.Yang,Y.Wang,Y.Qin,Y.Chong,Q.Yang,G.Li,L.Zhang and W.Li,GreenChem.,2011,13,1352–1361；(b)S.Wittmann,A.R.N.Grass,W.J.Stark andO.Reiser,Angew. Chem.,Int.Ed.,2010,49,1867–1870；(c)K.V.S.Ranganath,J.Kloesges,A.H.and F.Glorius,Angew.Chem.,Int.Ed.,2010,49,7786–7789。

Claims (4)

1.吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂，其特征是用式(II)所示：
2.权利要求1的吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂的制备方法，其特征是包括如下步骤：
氮气保护下，将Grubbs II催化剂(III)、氯化亚铜和化合物(I)溶于二氯甲烷中，在搅拌下，加热回流，降温至室温，旋干，过色谱硅胶柱，向所述色谱硅胶柱内加入体积比为1:2的石油醚和二氯甲烷的混合液洗脱杂质，再加入二氯甲烷洗脱得到吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂(II)；
反应式如下：
所述Grubbs II催化剂的结构见(III)：
3.根据权利要求2所述的制备方法，其特征是所述Grubbs II催化剂(III)，氯化亚铜和化合物(I)的摩尔比为1:1:1.25。
4.权利要求1的吲哚[3,2-a]恶唑烷标记的钌卡宾催化剂在催化闭环和交叉复分解反应中的应用。
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1582541A2 (en) * 2004-03-24 2005-10-05 Construction Research & Technology GmbH Silane-Terminated Polyurethanes with high stregth and high elongation
CN101230076A (zh) * 2007-09-30 2008-07-30 赢创德固赛有限责任公司 含有n杂环卡宾配体的钌的同核双金属和异核双金属亚烷基配合物及其用途
CN101990543A (zh) * 2008-04-08 2011-03-23 赢创德固赛有限公司 制备钌卡宾络合物的方法
CN102476060A (zh) * 2010-11-24 2012-05-30 中国石油化工股份有限公司 一种烯烃复分解催化剂及其制备方法
CN102658206A (zh) * 2012-05-02 2012-09-12 天津大学 钌卡拜络合物催化剂及其制备方法和应用
CN103951541A (zh) * 2008-01-25 2014-07-30 波士顿学院董事会 用于催化包括对映选择性烯烃复分解的复分解反应的方法
CN105979959A (zh) * 2013-08-09 2016-09-28 阿德利克斯公司 用于抑制磷酸盐转运的化合物和方法
CN106279297A (zh) * 2016-08-08 2017-01-04 苏州大学 基于亚磷酸酯和不饱和氮杂环卡宾的混配型镍(ii)配合物、其制备方法与应用

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1582541A2 (en) * 2004-03-24 2005-10-05 Construction Research & Technology GmbH Silane-Terminated Polyurethanes with high stregth and high elongation
CN101230076A (zh) * 2007-09-30 2008-07-30 赢创德固赛有限责任公司 含有n杂环卡宾配体的钌的同核双金属和异核双金属亚烷基配合物及其用途
CN103951541A (zh) * 2008-01-25 2014-07-30 波士顿学院董事会 用于催化包括对映选择性烯烃复分解的复分解反应的方法
CN101990543A (zh) * 2008-04-08 2011-03-23 赢创德固赛有限公司 制备钌卡宾络合物的方法
CN102476060A (zh) * 2010-11-24 2012-05-30 中国石油化工股份有限公司 一种烯烃复分解催化剂及其制备方法
CN102658206A (zh) * 2012-05-02 2012-09-12 天津大学 钌卡拜络合物催化剂及其制备方法和应用
CN105979959A (zh) * 2013-08-09 2016-09-28 阿德利克斯公司 用于抑制磷酸盐转运的化合物和方法
CN106279297A (zh) * 2016-08-08 2017-01-04 苏州大学 基于亚磷酸酯和不饱和氮杂环卡宾的混配型镍(ii)配合物、其制备方法与应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GUMBLEY PATRICIA等: ""Reversible Photochemical Tuning of Net Charge Separation from Contact Electri"", 《ACS APPLIED MATERIAL & INTERFACES》 *
YULIAN DUAN等: ""Highly efficient nitrogen chelated ruthenium"", 《DALTON TRANSACTIONS》 *

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